ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-4135-2011 Secondary aerosol formation from photochemical aging of aircraft exhaust in a smog chamber Miracolo M. A. 1 Hennigan C. J. 1 Ranjan M. 1 Nguyen N. T. 1 Gordon T. D. 1 Lipsky E. M. 2 Presto A. A. 1 Donahue N. M. 1 Robinson A. L. 1 Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, PA, 15213, USA Penn State Greater Allegheny, McKeesport, PA, 15123, USA 05 05 2011 11 9 4135 4147 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/11/4135/2011/acp-11-4135-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/4135/2011/acp-11-4135-2011.pdf

Field experiments were performed to investigate the effects of photo-oxidation on fine particle emissions from an in-use CFM56-2B gas turbine engine mounted on a KC-135 Stratotanker airframe. Emissions were sampled into a portable smog chamber from a rake inlet installed one-meter downstream of the engine exit plane of a parked and chocked aircraft. The chamber was then exposed to sunlight and/or UV lights to initiate photo-oxidation. Separate tests were performed at different engine loads (4, 7, 30, 85 %). Photo-oxidation created substantial secondary particulate matter (PM), greatly exceeding the direct PM emissions at each engine load after an hour or less of aging at typical summertime conditions. After several hours of photo-oxidation, the ratio of secondary-to-primary PM mass was on average 35 ± 4.1, 17 ± 2.5, 60 ± 2.2, and 2.7 ± 1.1 for the 4, 7, 30, and 85 % load experiments, respectively. The composition of secondary PM formed strongly depended on load. At 4 % load, secondary PM was dominated by secondary organic aerosol (SOA). At higher loads, the secondary PM was mainly secondary sulfate. A traditional SOA model that accounts for SOA formation from single-ring aromatics and other volatile organic compounds underpredicts the measured SOA formation by ~60 % at 4 % load and ~40 % at 85 % load. Large amounts of lower-volatiliy organic vapors were measured in the exhaust; they represent a significant pool of SOA precursors that are not included in traditional SOA models. These results underscore the importance of accounting for atmospheric processing when assessing the influence of aircraft emissions on ambient PM levels. Models that do not account for this processing will likely underpredict the contribution of aircraft emissions to local and regional air pollution.

 References % vor jede Referenz Agrawal, H., Sawant, A. A., Jansen, K., Wayne Miller, J., and Cocker, D. R.: Characterization of chemical and particulate emissions from aircraft engines, Atmos. Environ., 42, 4380–4392, 2008. Aiken, A. C., Decarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Docherty, K. S., Ulbrich, I. M., Mohr, C., Kimmel, J. R., Sueper, D., Sun, Y., Zhang, Q., Trimborn, A., Northway, M., Ziemann, P. J., Canagaratna, M. R., Onasch, T. B., Alfarra, M. R., Prevot, A. S., Dommen, J., Duplissy, J., Metzger, A., Baltensperger, U., and Jimenez, J. L.: O/c and om/oc ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry, Environ. Sci. Technol., 42, 4478–4485, 2008. Allan, J. D., Delia, A. E., Coe, H., Bower, K. N., Alfarra, M. R., Jimenez, J. L., Middlebrook, A. M., Drewnick, F., Onasch, T. B., Canagaratna, M. R., Jayne, J. T., and Worsnopf, D. R.: A generalised method for the extraction of chemically resolved mass spectra from aerodyne aerosol mass spectrometer data, J. Aerosol Sci., 35, 909–922, http://dx.doi.org/10.1016/J.Jaerosci.2004.02.007doi:10.1016/J.Jaerosci.2004.02.007, 2004. An, W. J., Pathak, R. K., Lee, B.-H., and Pandis, S. N.: Aerosol volatility measurement using an improved thermodenuder: Application to secondary organic aerosol, J. Aerosol Sci., 38, 305–314, 2007. Anderson, B. E., Chen, G., and Blake, D. R.: Hydrocarbon emissions from a modern commercial airliner, Atmos. Environ., 40, 3601–3612, 2006. Carslaw, D. C., Beevers, S. D., Ropkins, K., and Bell, M. C.: Detecting and quantifying aircraft and other on-airport contributions to ambient nitrogen oxides in the vicinity of a large international airport, Atmos. Environ., 40, 5424–5434, 2006. Chan, A. W. H., Kautzman, K. E., Chhabra, P. S., Surratt, J. D., Chan, M. N., Crounse, J. D., Kürten, A., Wennberg, P. O., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs), Atmos. Chem. Phys., 9, 3049–3060, http://dx.doi.org/10.5194/acp-9-3049-2009doi:10.5194/acp-9-3049-2009, 2009. Chirico, R., DeCarlo, P. F., Heringa, M. F., Tritscher, T., Richter, R., Prévôt, A. S. H., Dommen, J., Weingartner, E., Wehrle, G., Gysel, M., Laborde, M., and Baltensperger, U.: Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments, Atmos. Chem. Phys., 10, 11545–11563, http://dx.doi.org/10.5194/acp-10-11545-2010doi:10.5194/acp-10-11545-2010, 2010. DeCarlo, P., Slowik, J., Worsnop, D., Davidovits, P., and Jimenez, J.: Particle morphology and density characterization by combined mobility and aerodynamic diameter measurements. Part 1: Theory, Aerosol Sci. Technol., 38, 1185–1205, 2004. Dodson, R. E., Andres Houseman, E., Morin, B., and Levy, J. I.: An analysis of continuous black carbon concentrations in proximity to an airport and major roadways, Atmos. Environ., 43, 3764–3773, 2009. Grieshop, A. P., Donahue, N. M., and Robinson, A. L.: Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 2: analysis of aerosol mass spectrometer data, Atmos. Chem. Phys., 9, 2227–2240, http://dx.doi.org/10.5194/acp-9-2227-2009doi:10.5194/acp-9-2227-2009, 2009a. Grieshop, A. P., Logue, J. M., Donahue, N. M., and Robinson, A. L.: Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution, Atmos. Chem. Phys., 9, 1263–1277, http://dx.doi.org/10.5194/acp-9-1263-2009doi:10.5194/acp-9-1263-2009, 2009b. Herndon, S. C., Rogers, T., Dunlea, E. J., Jayne, J. T., Miake-Lye, R., and Knighton, B.: Hydrocarbon emissions from in-use commercial aircraft during airport operations, Environ. Sci. Technol., 40, 4406–4413, http://dx.doi.org/10.1021/es051209ldoi:10.1021/es051209l, 2006. Herndon, S. C., Wood, E. C., Northway, M. J., Miake-Lye, R., Thornhill, L., Beyersdorf, A., Anderson, B. E., Dowlin, R., Dodds, W., and Knighton, W. B.: Aircraft hydrocarbon emissions at oakland international airport, Environ. Sci. Technol., 43, 1730–1736, http://dx.doi.org/10.1021/es801307mdoi:10.1021/es801307m, 2009. Hildebrandt, L., Donahue, N. M., and Pandis, S. N.: High formation of secondary organic aerosol from the photo-oxidation of toluene, Atmos. Chem. Phys., 9, 2973–2986, http://dx.doi.org/10.5194/acp-9-2973-2009doi:10.5194/acp-9-2973-2009, 2009. Hu, S., Fruin, S., Kozawa, K., Mara, S., Winer, A. M., and Paulson, S. E.: Aircraft emission impacts in a neighborhood adjacent to a general aviation airport in southern california, Environ. Sci. Technol., 43, 8039–8045, 10.1021/es900975f, 2009. Huffman, J. A., Ziemann, P. J., Jayne, J. T., Worsnop, D. R., and Jimenez, J. L.: Development and characterization of a fast-stepping/scanning thermodenuder for chemically-resolved aerosol volatility measurements, Aerosol Sci. Technol., 42, 395–407, 2008. Huffman, J. A., Docherty, K. S., Aiken, A. C., Cubison, M. J., Ulbrich, I. M., DeCarlo, P. F., Sueper, D., Jayne, J. T., Worsnop, D. R., Ziemann, P. J., and Jimenez, J. L.: Chemically-resolved aerosol volatility measurements from two megacity field studies, Atmos. Chem. Phys., 9, 7161–7182, http://dx.doi.org/10.5194/acp-9-7161-2009doi:10.5194/acp-9-7161-2009, 2009. Kinsey, J. S., Dong, Y., Williams, D. C., and Logan, R.: Physical characterization of the fine particle emissions from commercial aircraft engines during the aircraft particle emissions experiment (apex) 1–3, Atmos. Environ., 44, 2147–2156, 2010. Liu, P. S. K., Deng, R., Smith, K. A., Williams, L. R., Jayne, J. T., Canagaratna, M. R., Moore, K., Onasch, T. B., Worsnop, D. R., and Deshler, T.: Transmission efficiency of an aerodynamic focusing lens system: Comparison of model calculations and laboratory measurements for the aerodyne aerosol mass spectrometer, Aerosol Sci. Technol., 41, 721–733, http://dx.doi.org/10.1080/02786820701422278doi:10.1080/02786820701422278, 2007. Matsunaga, A. and Ziemann, P.: Gas-wall partitioning of organic compounds in a teflon film chamber and potential effects on reaction product and aerosol yield measurements, Aerosol Sci. Technol., 44, 881–892, 2010. Murphy, B. N. and Pandis, S. N.: Simulating the formation of semivolatile primary and secondary organic aerosol in a regional chemical transport model, Environ. Sci. Technol., 43, 4722–4728, http://dx.doi.org/10.1021/es803168adoi:10.1021/es803168a, 2009. Ng, N. L., Kroll, J. H., Chan, A. W. H., Chhabra, P. S., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from m-xylene, toluene, and benzene, Atmos. Chem. Phys., 7, 3909–3922, http://dx.doi.org/10.5194/acp-7-3909-2007doi:10.5194/acp-7-3909-2007, 2007. Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., Flagan, R. C., and Seinfeld, J. H.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, http://dx.doi.org/10.1021/es950943+doi:10.1021/es950943+, 1996. Onasch, T. B., Jayne, J. T., Herndon, S., Worsnop, D. R., Miake-Lye, R. C., Mortimer, I. P., and Anderson, B. E.: Chemical properties of aircraft engine particulate exhaust emissions, Journal of Propulsion and Power, 25, 1121–1137, http://dx.doi.org/10.2514/1.36371doi:10.2514/1.36371, 2009. Petzold, A. and Schröder, F. P.: Jet engine exhaust aerosol characterization, Aerosol Sci. Technol., 28, 62–76, 1998. Presto, A. A., Nguyen, N., Ranjan, M., Reeder, A., Lipsky, E. M., Hennigan, C. J., Miracolo, M. A., and Robinson, A. L.: Fine particle and organic vapor emissions from staged tests of an in-use aircraft engine, Atmos. Environ, http://dx.doi.org/10.1016/j.atmosenv.2011.03.061doi:10.1016/j.atmosenv.2011.03.061, in press, 2011. Robinson, A. L., Grieshop, A. P., Donahue, N. M., and Hunt, H. W.: Updating our conceptual model for fine particle mass emissions from combustion systems, J. Air Waste Manage. Assoc., 60, 1204–1222, 2010. Sage, A. M., Weitkamp, E. A., Robinson, A. L., and Donahue, N. M.: Evolving mass spectra of the oxidized component of organic aerosol: results from aerosol mass spectrometer analyses of aged diesel emissions, Atmos. Chem. Phys., 8, 1139–1152, http://dx.doi.org/10.5194/acp-8-1139-2008doi:10.5194/acp-8-1139-2008, 2008. Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics: from Air Pollution to Climate Change, John Wiley, New York, USA, 1185, 2006 Slemr, F., Giehl, H., Slemr, J., Busen, R., Schulte, P., and Haschberger, P.: In-flight measurement of aircraft non-methane hydrocarbon emission indices, Geophys. Res. Lett., 25, 321–324, http://dx.doi.org/10.1029/97gl03784doi:10.1029/97gl03784, 1998. Spicer, C. W., Holdren, M. W., Riggin, R. M., and Lyon, T. F.: Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines, Ann. Geophys., 12, 944–955, http://dx.doi.org/10.1007/s00585-994-0944-0doi:10.1007/s00585-994-0944-0, 1994. Unal, A., Hu, Y., Chang, M. E., Talat Odman, M., and Russell, A. G.: Airport related emissions and impacts on air quality: Application to the atlanta international airport, Atmos. Environ., 39, 5787–5798, 2005. Weitkamp, E. A., Sage, A. M., Pierce, J. R., Donahue, N. M., and Robinson, A. L.: Organic aerosol formation from photochemical oxidation of diesel exhaust in a smog chamber, Environ Sci Technol, 41, 6969–975, 2007. Wood, E. C., Herndon, S. C., Timko, M. T., Yelvington, P. E., and Miake-Lye, R. C.: Speciation and chemical evolution of nitrogen oxides in aircraft exhaust near airports, Environ. Sci. Technol., 42, 1884–1891, http://dx.doi.org/10.1021/es072050adoi:10.1021/es072050a, 2008. Yu, K. N., Cheung, Y. P., Cheung, T., and Henry, R. C.: Identifying the impact of large urban airports on local air quality by nonparametric regression, Atmos. Environ., 38, 4501–4507, 2004. Zhang, Q., Alfarra, M. R., Worsnop, D. R., Allan, J. D., Coe, H., Canagaratna, M. R., and Jimenez, J. L.: Deconvolution and quantification of hydrocarbon-like and oxygenated organic aerosols based on aerosol mass spectrometry, Environ. Sci. Technol., 39, 4938–4952, 2005.